Conductive particle dispersion and its manufacturing method, coating liquid for forming conductive film and substrate with conductive coating

Abstract

This invention relates to a dispersion of conductive particles containing antimony-doped tin oxide. The conductive particles comprise clusters of chain-like particles formed by the connection of primary particles. The dispersion contains 1% to 20% by mass of the conductive particles and, relative to the content of the conductive particles, contains 0.05% to 0.5% by mass of a cluster-forming agent. In the particle size distribution of this dispersion, measured using a dynamic light scattering particle size analyzer, the volume average particle size is 10 nm to 50 nm; the difference between the particle size D16 accumulated to 16% and the particle size D84 accumulated to 84% (D84-D16) based on volume is 3 nm to 50 nm. Low resistivity conductive films can be achieved using such conductive particles.

Description

Technical field

[0001] The present invention relates to a dispersion liquid containing conductive chain particles, a coating liquid for forming a conductive film prepared using the dispersion liquid, and a substrate with a conductive film.

Prior technology

[0002] Conventionally, a conductive film is formed on a substrate using a coating solution containing conductive particles. Transparent conductive films are used in display devices, touch panels, solar cells, and the like. In order to achieve both transparency and low resistance of the conductive film, a coating liquid containing chain-shaped conductive particles was used. For example, in JP-A-2019-157026 (Patent Document 1), a coating liquid containing an alkoxysilane oligomer that is easily bonded to chain-shaped conductive particles as a binder component is known in order to increase the strength of the film. .

[0003] Furthermore, in Japanese Patent Application Laid-Open No. 2006-339113 (Patent Document 2), it is known to use chain particles to obtain a film excellent in antistatic and electromagnetic wave shielding. In Patent Document 2, the primary particles are arranged in a chain by adjusting the pH after the ion exchange treatment of the dispersion liquid of the conductive primary particles, and the primary particles are hydrolyzed by adding alcohol to make the primary particles Linking process to create chain-like particles.

Content of invention

[0004] In the coating solution of Patent Document 1, the insulating binder component gradually covers the surface of the chain-shaped conductive particles, and when forming a film, there is a structure in which the insulating component exists between the chain-shaped conductive particles, so it is difficult to form a multi-layer structure. a conductive path. That is, there is a technical problem that the conductivity decreases with time, and the same conductivity as that of the film formed from the initial coating liquid cannot be obtained.

[0005] Furthermore, in recent years, low resistance of conductive films has been demanded, and the chain-shaped conductive particles disclosed in Patent Document 1 and Patent Document 2 cannot achieve both low resistance and high hardness.

[0006] Accordingly, an object of the present invention is to provide conductive particles capable of reducing the resistance of a conductive film.

[0007] The present invention relates to a dispersion of conductive particles containing antimony-doped tin oxide (ATO). The conductive particles include clusters of chain-like particles formed by connecting primary particles. The dispersion contains 1% by mass to 20% by mass of conductive particles, and 0.05% to 0.5% by mass of a cluster forming agent relative to the content of the conductive particles. In the particle size distribution of the dispersion liquid measured by a dynamic light scattering particle size distribution meter, the volume average particle size is 10nm~50nm; based on the volume, the particle size D16 when accumulating from the small particle size side to 16% The difference (D84-D16) from the particle size D84 when the accumulation reaches 84% ​​is 3nm~50nm. A cluster forming agent is added to cluster the chain-like particles. As a cluster forming agent, an acid or a polymer coagulant is used.

[0008] In addition, the method for producing a dispersion of conductive particles according to the present invention includes the step of preparing a dispersion of chain particles connected by primary particles, the primary particles containing ATO; The process of adding 0.05%~0.5% mass of dispersant to the sum of the mass of conductive particles existing in the state of primary particles and the mass of conductive particles existing in the state of chain particles.

Implementation

[0010] The present invention is a dispersion of conductive particles containing ATO, and the conductive particles include clusters of chain-like particles formed by linking primary particles. The dispersion liquid contains 1% by mass to 20% by mass of conductive particles, and contains 0.05% by mass to 0.5% by mass of a cluster forming agent relative to the content of the conductive particles. When measuring the particle size distribution of the dispersion liquid with a dynamic light scattering particle size distribution meter, the volume average particle size is 10nm~50nm; based on the volume, the particle size D16 when accumulating from the small particle size side to 16% The difference (D84-D16) from the particle size D84 when the accumulation reaches 84% ​​is 3nm~50nm. In addition, hereafter, this particle diameter difference (D84-D16) is called the width|variety of particle diameter distribution. In this case, the average particle diameter of the primary particles is preferably 3 nm to 10 nm.

[0011] If the conductive particles exceed 20% by mass, it is difficult to form a cluster of an appropriate size, and it is also difficult to exist stably in its size. When it is less than 1% by mass, the amount of conductive particles is too small to be practical. In addition, in order to form clusters, the cluster forming agent needs to be 0.05% by mass or more of the conductive particle content, and if it exceeds 0.5%, the conductivity may be significantly reduced.

[0012] From the particle size distribution determined by the dynamic light scattering method, it can be known how the clusters formed by the chain-like particles are present. That is, if a large number of clusters are present, the volume average particle diameter becomes large, and the particle diameter distribution also becomes broad. If the volume average particle diameter and the width of the particle diameter distribution are within the above-mentioned ranges, the effect due to the presence of clusters can be obtained. For example, low resistance can be achieved because conductive paths are well formed. In a coating liquid using such a dispersion liquid, the contact (reaction) area of ​​the conductive particles with other components (binder, etc.) is small, so changes over time are suppressed. Since the size of clusters is controlled in the film obtained by this coating solution, light scattering (haze) can be suppressed without impairing optical properties.

[0013] Further, relative to the content of the conductive particles, the cluster structure is fixed by adding 3% to 25% by mass of alkoxysilane. Therefore, even if the dispersion liquid is stirred and ultrasonic waves are applied (ultrasonic wave application), the clusters are difficult to redisperse. If the amount of alkoxysilane is too small, there is a possibility that clusters cannot be immobilized. In addition, when the amount is too large, the alkoxysilane may cover the surface of the cluster excessively, which may lower the conductivity. The added amount of alkoxysilane is preferably 3%~15%. Alkoxysilane is usually represented by "R1n-Si(OR2)4-n [Formula 1]". Herein, R1 and R2 are a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 10 carbons, and they may be the same or different from each other. In addition, n is an integer of 0-3. Specific examples of alkoxysilanes are shown in Table 1.

[0014] [Table 1] Alkoxysilane n=0 Tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane n=1 Methyltrimethoxysilane, Methyltriethoxysilane, Methyltriacetoxysilane, Methyltripropoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltriacetoxysilane, Phenyltrimethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Phenyltriacetyloxysilane, γ-chloropropyltrimethoxysilane, γ-Chloropropyltriethoxysilane, γ-Chloropropyltripropoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ-Glycidoxypropyltriethoxysilane, γ-(β-Glycidoxyethoxy)propyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Aminopropyltrimethoxysilane, Trialkoxy or triacyloxysilanes such as γ-mercaptopropyltriethoxysilane n=2 Dimethyldimethoxysilane, Dimethyldiethoxysilane, Phenylmethyldiethoxysilane, γ-Glycidoxypropylmethyldimethoxysilane, γ-Glycidoxypropylphenyldiethoxysilane, γ-Chloropropylmethyldimethoxysilane, Dimethyldiacetoxysilane, γ-Methacryloxypropylmethyldimethoxysilane, γ-Mercaptopropylmethyldimethoxysilane, γ-Aminopropylmethyldimethoxysilane and other dialkoxysilanes or diacyloxysilanes n=3 Trimethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane and other monoalkoxysilanes

[0015] In addition, the chain particle is a particle in which three or more primary particles containing ATO as a component are linked in a chain. Particles can have branched connected parts. That is, the main chain part has a structure in which three or more primary particles are connected, and branch parts may exist. Primary particles are inorganic particles in a monodisperse state. The average particle diameter of the primary particles is preferably 3 nm to 10 nm. The particle diameters of arbitrary 100 primary particles were measured from an image taken with a transmission electron microscope (TEM), and the average value thereof was defined as the average particle diameter of the primary particles. In addition, 50 arbitrary particles were selected from this image, and the number of connections of each particle was measured. The average value of the number of connections of 50 particles is the average number of connections. The average number of connections is preferably 3 or more, particularly preferably 5 or more. When the average connection number of primary particles is small, there is a possibility that the effect of improving electrical conductivity cannot be sufficiently obtained. If the average particle size is too small, the crystallinity will be low, and there is a possibility that the conductivity of the primary particles themselves cannot be sufficiently obtained. Conversely, if the average particle diameter is too large, it becomes difficult to develop a chain structure, and even if it becomes a chain, it becomes difficult to effectively form a conductive path, and there is a possibility that sufficient conductivity of the film cannot be obtained. Elements other than antimony and tin oxide may be included in the primary particles as long as they do not significantly impede conductivity.

[0016] Next, a method for producing a dispersion of conductive particles will be described. First, a dispersion of chain-like particles formed by linking primary particles containing ATO is prepared. The dispersion of chain-shaped particles can be prepared by a known method such as the method disclosed in JP-A-2006-339113. 0.05% to 0.5% by mass of a cluster forming agent is added to the dispersion liquid of the conductive particle component (the total amount of the conductive particles present as primary particles and the conductive particles present as chain particles in the dispersion liquid). As a result, clusters of chain-like particles are formed. The cluster structure can be controlled by the concentration of chain particles in the dispersion, pH, temperature, and stirring time. Through the cluster forming agent, the chain particles form three-dimensional clusters through two-dimensional and three-dimensional connections. Acids and polymer coagulants can be used as the cluster forming agent. Examples of polymer coagulants include nonionic, anionic, cationic, amphoteric, polyamine and dicyandiamide coagulants. The appropriate addition amount differs depending on the type of cluster forming agent. Examples of the acid include organic acids such as formic acid, acetic acid, citric acid, and benzoic acid; and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydroiodic acid, and tetrafluoroboric acid. Hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, which are easily soluble in water and readily available industrially, are preferred.

[0017] <coating solution>

[0018] A binder component and a solvent are added to such a dispersion liquid of conductive particles to prepare a coating liquid. That is, the coating liquid of this invention contains the conductive particle containing ATO, an alkoxysilane oligomer (binder component), and a solvent. The conductive particles include clusters of chain-like particles formed by linking primary particles. The coating solution contains 0.05% to 0.5% by mass of the conductive particle content of the cluster forming agent and 25% to 300% by mass of the conductive particle content of the alkoxysilane oligomer. In the particle size distribution of the coating solution measured with a dynamic light scattering particle size distribution meter, the volume average particle size is 70nm~600nm; the particle size when the particle size is accumulated from the small side to 16% based on volume The difference (D84-D16) between D16 and D84 when the particle size reaches 84% ​​is 60nm~800nm. When a binder component and a solvent are added to the dispersion liquid of conductive particles, the clusters coagulate more slowly to form a large structure (floculation (フロキュレート)). Therefore, in the measurement by the dynamic light scattering method, the volume average particle diameter and the width of the particle diameter distribution become larger than those of the above-mentioned dispersion liquid.

[0019] After coating, the solvent used herein can be removed by a drying process or the like. Hydrophilic organic solvents such as alcohols, glycols, glycol ethers, and ketones that do not hinder cluster structure control are suitable. Specifically, 1-methoxy-2-propanol, diacetone alcohol, ethylene glycol, diethylene glycol, methanol, ethanol, isopropanol, and acetone can be exemplified.

[0020] The weight average molecular weight of the alkoxysilane oligomer is preferably 1000-20000. The alkoxysilane oligomer is a hydrolyzed polymer of alkoxysilane represented by the above "Formula 1", wherein n is an integer of 0-2. In the case where n is 3, oligomers cannot be formed because they can only be combined between two molecules. The smaller n is, the more preferable it is, and it is most preferable to use an alkoxysilane in which n is 0. When such an alkoxysilane is used, organic components that are difficult to conduct electricity between clusters are reduced, and high conductivity is obtained.

[0021] Furthermore, as described above, the coating solution contains an alkoxysilane oligomer in an amount of 25% to 300% by mass of the conductive particle content. That is, the mass ratio of the conductive particle and the alkoxysilane oligomer is in the range of 80:20 to 25:75. If there are few alkoxysilane oligomers, the binder component will decrease, and sufficient film hardness may not be obtained. In addition, if too much, the reaction with the surface of the particles constituting the cluster in the coating liquid proceeds excessively, and the storage stability of the coating liquid may be lowered.

[0022] Hereinafter, embodiments of the present invention will be described in detail.

[0023] embodiment

[0024] [Example 1]

[0025] First, an aqueous dispersion containing ATO particles (primary particles) (average particle diameter of ATO particles: 5 nm, solid content concentration: 20.0% by mass, pH: 6.9) was prepared. An amphoteric ion exchange resin corresponding to 40% by mass of the solid content of the ATO particles was added to this dispersion, and stirred at 25° C. for 2 hours. Afterwards, the amphoteric ion exchange resin is separated using a metal mesh. As a result, the ATO particles are connected in chains, and an aqueous dispersion of chain particles is obtained.

[0026] The solid content concentration of the aqueous dispersion of the chain particles was diluted with pure water to 5% by mass. To 100.0 g of this aqueous dispersion, 0.5 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent, followed by stirring at 25° C. for 5 minutes. Thereby, the chain-like particles form clusters, and the dispersion liquid of the conductive particles of the present invention is obtained.

[0027] <coating solution>

[0028] A coating liquid is prepared by adding a binder component and a solvent to the dispersion liquid of the conductive particles. In this example, 2.7 g of pure water was added while stirring 60.3 g of a dispersion liquid of conductive particles at 25°C. Next, 17.0 g of Solmix AP-11 (alcohol mixed solvent containing ethanol as a main solvent) was added. After stirring for 5 minutes, 20.0 g of the binder component was added while being stirred. And after stirring at 25 degreeC for 15 minutes, the coating liquid was obtained by filtration. Here, as the binder component, an ethanol dispersion of an alkoxysilane oligomer with a molecular weight of 4980 (solid content concentration: 9.9% by mass) obtained by hydrolyzing tetramethoxysilane was used.

[0029] <film substrate>

[0030] The coating liquid was coated on a glass substrate by a bar coating method, and dried at 80° C. for 1 minute. Furthermore, it heated for 30 minutes in the dryer of 130 degreeC. Thus, a film-coated substrate was obtained.

[0031] Table 2 and Table 3 show the preparation conditions of the dispersion liquid and coating liquid of conductive particles. In addition, the measurement results of the following physical properties are also shown in the same table. In addition, Examples and Comparative Examples described later were also performed in the same manner.

[0032] (1) Determination of the concentration of conductive particles and the amount of conductive particles

[0033] The dispersion liquid was weighed into a magnetic crucible, heated at 1000° C. for a certain period of time, and based on the weight ratio before and after heating, the solid content concentration of the conductive particles was obtained.

[0034] When the dispersion of conductive particles contains solids other than the ATO component, the dispersion can be measured using an inductively coupled plasma emission spectrometer to obtain the amount of each element contained in the dispersion , to determine the amount of conductive particles.

[0035] (2) content of cluster forming agent in the dispersion

[0036] The dispersion liquid is centrifuged to separate the conductive particles and the supernatant. Elements contained in the supernatant and their contents were measured using an ICP emission spectrometer. This result was compared with a reference obtained by analyzing the cluster-forming agent in the same manner in advance, and the cluster-forming agent contained in the supernatant and its content were determined.

[0037] (3) volume average particle size, particle size distribution width

[0038] Use the dynamic light scattering method particle size distribution meter (NANOTRAC Wave 2-UT151 manufactured by MICROTRAC Corporation) to measure the dispersion liquid, and obtain the average particle diameter and the width of the particle diameter distribution of the dispersion liquid (particle diameter difference: D84-D16 ).

[0039] (4) pencil hardness

[0040] Using a pencil specified in JIS S-6006, the pencil hardness of the film-coated substrate was measured with a surface property measuring machine (Tray Bogia, manufactured by Shinto Scientific Co., Ltd.). According to the operation manual of the measuring machine, a load of 500 g was applied to the surface with a pencil of each hardness, and scanning was performed. Scan traces were confirmed, and the highest hardness value at which no flaws were observed was defined as the pencil hardness value.

[0041] (5) surface resistance and storage stability

[0042] Using a surface resistance measuring machine (Hyrester UX MCP-HT800 manufactured by Mitsubishi Chemical Analitec Co., Ltd.), the surface resistance of the film-coated substrate prepared using the coating liquid just prepared was measured. Next, this coating liquid was left still for 24 hours in a bathtub whose water temperature was adjusted to 40°C. Using this heat-treated coating solution, a film-coated substrate was produced in the same manner, and the surface resistance was measured. Storage stability was evaluated based on the rate of change in surface resistance (surface resistance value of film-coated substrate obtained from coating solution after heating treatment / surface resistance value of film-coated substrate obtained from initial coating solution).

[0043] In the following description, points different from Embodiment 1 are described.

[0044] [Example 2]

[0045] In this example, as a cluster forming agent, polyaluminum chloride (manufactured by Taki Chemical Co., Ltd., overbased aluminum chloride PAC#1000) was used. The concentration was diluted with pure water to 0.2% by mass, and 5.0 g of the diluted solution was added.

[0046] <coating solution>

[0047] Without adding pure water to 63.0 g of the dispersion liquid of conductive particles, it was stirred at 25°C.

[0048] [embodiment 3]

[0049] In this example, polyethyleneimine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average molecular weight: 600) was used as the cluster forming agent. The concentration was diluted to 2.0% by mass with pure water, and 0.8 g of the diluted solution was added.

[0050] <coating solution>

[0051] 2.6 g of pure water was added to 60.5 g of the dispersion liquid of the conductive particles.

[0052] [Example 4]

[0053] In this example, the aqueous dispersion of chain-shaped particles was diluted with pure water so that the solid content concentration was 10.0% by mass. Furthermore, the addition amount of hydrochloric acid (concentration: 1.0 mass %) was set to 1.0 g, and it stirred at 25 degreeC for 5 minutes. Further, tetramethoxysilane is added to immobilize the cluster structure. Here, 4.9 g of the alkoxysilane oligomer used as the binder component in Example 1 was added, and it stirred at 25 degreeC for 1 hour. Except for this, a dispersion liquid of conductive particles was prepared in the same manner as in Example 1.

[0054] <coating solution>

[0055] In addition, the dispersion was 32.3 g, the added amount of pure water was 30.7 g, the added amount of the solvent (AP-11) was 18.6 g, and the binder component was 18.4 g.

[0056] [Example 5]

[0057] In this embodiment, the amount of alkoxysilane oligomer added to immobilize the cluster structure is 24.5 g. Except for this, a dispersion liquid of conductive particles was prepared in the same manner as in Example 4.

[0058] <coating solution>

[0059] In addition, the dispersion liquid was 38.0 g, the added amount of pure water was 25.0 g, the added amount of the solvent (AP-11) was 24.5 g, and the added amount of the binder component was 12.5 g.

[0060] [Example 6]

[0061] In this example, the aqueous dispersion of chain particles was diluted with pure water so that the solid content concentration was 20.0% by mass. To 100.0 g of this dispersion liquid, 1.0 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent.

[0062] <coating solution>

[0063] The dispersion of conductive particles was 15.2 g, and the amount of pure water added was 47.9 g.

[0064] [Example 7]

[0065] In this example, the aqueous dispersion of chain particles was diluted with pure water so that the solid content concentration was 15.0% by mass. To 100.0 g of this dispersion liquid, 1.5 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent.

[0066] <coating solution>

[0067] The dispersion of conductive particles was 20.3 g, and the amount of pure water added was 42.7 g.

[0068] [Embodiment 8]

[0069] In this example, the aqueous dispersion of chain particles was diluted with pure water so that the solid content concentration was 10.0% by mass. To 100.0 g of this dispersion liquid, 1.0 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent.

[0070] <coating solution>

[0071] The dispersion of conductive particles was 30.3 g, and the amount of pure water added was 32.7 g.

[0072] [Example 9]

[0073] In this example, the aqueous dispersion of chain particles was diluted with pure water so that the solid content concentration was 10.0% by mass. To 100.0 g of this dispersion liquid, 1.0 g of phosphoric acid (concentration: 1.0% by mass) was added as a cluster forming agent.

[0074] <coating solution>

[0075] The dispersion of conductive particles was 30.3 g, and the amount of pure water added was 32.7 g.

[0076] [Example 10]

[0077] In this example, the aqueous dispersion of chain particles was diluted with pure water so that the solid content concentration was 10.0% by mass. To 100.0 g of this dispersion liquid, 1.0 g of nitric acid (concentration: 1.0% by mass) was added as a cluster forming agent.

[0078] <coating solution>

[0079] The dispersion of conductive particles was 30.3 g, and the amount of pure water added was 32.7 g.

[0080] [Comparative Example 1]

[0081] In this comparative example, no chain particles were prepared, and the cluster forming agent was directly added to the ATO particles (primary particles). That is, to 100.0 g of the aqueous dispersion of ATO particles (solid content concentration: 20.0% by mass) as in Example 1, after adding 5.0 g of hydrochloric acid (concentration: 1.0% by mass) as a cluster forming agent, the dispersion increased in viscosity, turns into a gel. Therefore, a dispersion liquid and a coating liquid of conductive particles could not be obtained.

[0082] [Comparative Example 2]

[0083] In this comparative example, an aqueous dispersion of chain-like particles was prepared in the same manner as in Example 1, except that no cluster forming agent was used. The aqueous dispersion of the chain particles was 15.0 g, and the amount of pure water added was 48.0 g to prepare a coating liquid.

[0084] [Comparative Example 3]

[0085] In this comparative example, 3.0 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent. A coating liquid was prepared in the same manner as in Example 1 except that the dispersion liquid of conductive particles was 61.5 g and that the amount of pure water added was 1.5 g. However, aggregation occurred and it could not be used as a coating material.

[0086] [Comparative Example 4]

[0087] In this comparative example, as a cluster forming agent, the same polyaluminum chloride as in Example 2 was diluted with pure water, and 1.0 g of the diluted solution was added at a concentration of 5.0% by mass.

[0088] A coating liquid was prepared in the same manner as in Example 1, except that the conductive particle dispersion was 60.6 g and the amount of pure water added was 2.4 g. However, coagulation occurred and it could not be used as a coating.

[0089] [comparative example 5]

[0090] In this comparative example, the same polyethyleneimine as the cluster forming agent as in Example 3 was diluted with pure water, and 1.0 g of the diluted solution was added at a concentration of 5.0% by mass.

[0091] A coating liquid was prepared in the same manner as in Example 1, except that the conductive particle dispersion was 60.6 g and the amount of pure water added was 2.4 g. However, agglomeration occurred and it could not be used as a coating.

[0092] [Table 2] Adjustment method of conductive particle dispersion liquid Physical Properties of Conductive Particle Dispersion Dispersion of chain particles cluster former clustering conditions Fixation of cluster structures quality Solid content concentration Conductive particle composition quality type Addition amount of forming agent solution Concentration of forming agent Amount of former pH temperature Stiring time Alkoxysilane Raw Materials Solid content concentration Ratio of alkoxysilane to conductive particles Concentration of conductive particles Ratio of forming agent to conductive particles volume average particle size Distribution width D 84 -D 16 (g) quality% (g) (g) quality% (g) quality% quality% (nm) (nm) Example 1 100.0 5.0 5.0 hydrochloric acid 0.5 1.0 0.005 3.4 25°C 5 minutes none - - 4.9 0.10% 13.0 6.4 Example 2 100.0 5.0 5.0 PACs 5.0 0.2 0.01 3.2 25°C 5 minutes none - - 4.0 0.20% 30.0 17.0 Example 3 100.0 5.0 5.0 PEI 0.8 2.0 0.015 3.7 25°C 5 minutes none - - 4.8 0.30% 28.0 11.0 Example 4 100.0 10.0 10.0 hydrochloric acid 1.0 1.0 0.01 3.4 25°C 5 minutes ② 10.0 5% 9.5 0.10% 11.7 5.2 Example 5 100.0 10.0 10.0 hydrochloric acid 1.0 1.0 0.01 3.4 25°C 5 minutes ② 10.0 25% 9.5 0.10% 33.4 26.2 Example 6 100.0 20.0 20.0 hydrochloric acid 1.0 1.0 0.01 2.3 25°C 5 minutes none - - 19.0 0.05% 18.9 22.0 Example 7 100.0 15.0 15.0 hydrochloric acid 1.5 1.0 0.015 2.1 25°C 5 minutes none - - 14.0 0.10% 12.3 6.6 Example 8 100.0 10.0 10.0 hydrochloric acid 1.0 1.0 0.01 2.3 25°C 5 minutes none - - 9.5 0.10% 10.4 4.6 Example 9 100.0 10.0 10.0 phosphoric acid 1.0 1.0 0.01 2.4 25°C 5 minutes none - - 9.5 0.10% 11.1 5.3 Example 10 100.0 10.0 10.0 nitric acid 1.0 1.0 0.01 2.4 25°C 5 minutes none - - 9.5 0.10% 12.3 5.0 Comparative example 1 100* 20* 20* hydrochloric acid 5.0 1.0 0.05 - - - 16.0 0.25% - - Comparative example 2 100.0 5.0 5.0 - 0 0.0 0 - - - - - - 20.0 0% 8.7 1.4 Comparative example 3 100.0 5.0 5.0 hydrochloric acid 3.0 1.0 0.03 3.2 25°C 5 minutes none - - 4.3 0.60% 59.6 58.6 Comparative example 4 100.0 5.0 5.0 PACs 1.0 5.0 0.05 3.0 25°C 5 minutes none - - 4.8 1.00% 758 1210 Comparative Example 5 100.0 5.0 5.0 PEI 1.0 5.0 0.05 3.1 25°C 5 minutes none - - 4.8 1.00% 120 550 *Comparative Example 1 "Primary Particle Dispersion" only ②Tetramethoxysilane

[0093] [Table 3] Preparation of Coating Solution Physical Properties of Coating Liquid physical properties of the membrane Quality of conductive particle dispersion solvent Adhesive ingredients volume average particle size Distribution width D. 84 -D 16 pencil hardness surface resistance (A) surface resistance (B) surface resistance ratio (B / A) water Alcohol mixed solvent Raw material of oligomer Solid content concentration quality (g) (g) (g) (quality%) (g) (nm) (nm) (Ω / □) (Ω / □) Example 1 60.3 2.7 17.0 ② 10 20.0 81.1 62.2 4H 5.4E+07 5.0E+08 9.26 Example 2 63.0 0.0 17.0 ② 10 20.0 463.8 712.8 4H 6.2E+07 9.2E+08 14.84 Example 3 60.5 2.6 17.0 ② 10 20.0 389.9 325.8 4H 7.0E+07 1.0E+09 14.29 Example 4 32.3 30.7 18.6 ② 10 18.4 274.2 73.4 4H 9.4E+07 3.2E+09 34.04 Example 5 38.0 25.0 24.5 ② 10 12.5 511.4 710.8 4H 1.4E+08 1.9E+09 13.57 Example 6 15.2 47.9 17.0 ② 10 20.0 337.6 468.4 4H 4.4E+07 1.7E+09 38.64 Example 7 20.3 42.7 17.0 ② 10 20.0 270.6 370.2 4H 4.2E+07 1.5E+09 35.71 Example 8 30.3 32.7 17.0 ② 10 20.0 88.8 67.2 4H 5.5E+07 1.8E+09 32.73 Example 9 30.3 32.7 17.0 ② 10 20.0 91.7 64.4 4H 6.3E+07 5.1E+09 80.95 Example 10 30.3 32.7 17.0 ② 10 20.0 85.2 116 4H 6.5E+07 5.7E+09 87.69 Comparative example 1 - - - - - - - - - - - - Comparative example 2 15.0 48.0 17.0 ② 10 20.0 66.9 32.4 4H 5.0E+07 3.0E+10 600.00 Comparative example 3 61.5 1.5 17.0 ② 10 20.0 - - - - - - Comparative example 4 60.6 2.4 17.0 ② 10 20.0 - - - - - - Comparative Example 5 60.6 2.4 17.0 ② 10 20.0 - - - - - - ②: Tetramethoxysilane [Simple description of the diagram]

[0009] None.

Claims

1. A dispersion comprising conductive particles doped with antimony tin oxide, the conductive particles comprising clusters of chain-like particles formed by primary particles, the dispersion comprising 1% to 20% by mass of the conductive particles, and comprising 0.05% to 0.5% by mass of a clustering agent relative to the content of the conductive particles, wherein the volume average particle size is 10 nm to 50 nm in the particle size distribution of the dispersion as measured by a dynamic light scattering particle size analyzer; and the difference (D84-D16) between the particle size D16 accumulated to 16% and the particle size D84 accumulated to 84% (based on volume) is 3 nm to 50 nm, wherein the clustering agent is an acid or a polymeric agglomerant.

2. The dispersion as claimed in claim 1, wherein, The dispersion contains 3% to 15% by mass of alkoxysilane relative to the content of the conductive particles.

3. A method for manufacturing a dispersion of conductive particles, characterized in that the manufacturing method comprises: The process of preparing a dispersion of chain-like particles connected by primary particles, wherein the primary particles contain antimony-doped tin oxide. The step of adding 0.05% to 0.5% by mass of a clustering agent relative to the sum of the mass of conductive particles existing in the primary particle state and the mass of conductive particles existing in the chain particle state in the dispersion; wherein the clustering agent is an acid or a polymeric coagulant.

4. A coating solution comprising conductive particles containing antimony-doped tin oxide, an alkoxysilane oligomer, and a solvent for forming a conductive film, wherein the conductive particles comprise clusters of chain-like particles formed by the connection of primary particles, the coating solution contains 1% to 20% by mass of the conductive particles, and contains 0.05% to 0.5% by mass of a clustering agent and 25% to 300% by mass of the alkoxysilane oligomer, wherein the volume average particle size is 70 nm to 600 nm in the particle size distribution of the coating solution as measured by a dynamic light scattering particle size analyzer; and the difference between the particle size D16 accumulated to 16% and the particle size D84 accumulated to 84% (D84-D16) based on volume is 60 nm to 800 nm, wherein the clustering agent is an acid or a polymeric agglomerant.

5. A substrate with a conductive coating, characterized in that a film obtained by the coating liquid described in claim 4 is disposed on the substrate.